CN101559926B - Method for preparing zirconium hydride - Google Patents
Method for preparing zirconium hydride Download PDFInfo
- Publication number
- CN101559926B CN101559926B CN2008101042400A CN200810104240A CN101559926B CN 101559926 B CN101559926 B CN 101559926B CN 2008101042400 A CN2008101042400 A CN 2008101042400A CN 200810104240 A CN200810104240 A CN 200810104240A CN 101559926 B CN101559926 B CN 101559926B
- Authority
- CN
- China
- Prior art keywords
- hydride
- zirconium hydride
- zircoium hydride
- room temperature
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention relates to a method for preparing zirconium hydride, comprising the following steps: (1) ultrasonically washing the zirconium hydride for 15 minutes to 20 minutes by acetone and drying the zirconium hydride; (2) placing the zirconium hydride obtained in the step (1) into a stainless steel crucible and then into a vacuum tube type resistance furnace for pumping vacuum, charging carbondioxide into the crucible, heating the zirconium hydride to 350 DEG C to 600 DEG C from room temperature at the speed of 1 DEG C to 5 DEG C/min and insulating the zirconium hydride for 30 hours to 60 hours in the temperature range; and (3) cooling the zirconium hydride to the room temperature and forming a zirconium hydride film layer with a certain hydrogen permeation resistant function on the z irconium hydride surface. The zirconium hydride is arranged in the mixture atmosphere of oxidizing gas and inert gas to be heated, and a hydrogen evolution phenomenon of the zirconium hydride under the condition of high temperature can be effectively prevented by heating the zirconium hydride to 500 DEG C to 900 DEG C from the room temperature.
Description
Technical field
The present invention relates to a kind of preparation method of zircoium hydride, belong to the technical field of material protection.
Technical background
Zircoium hydride is piled ideal solid neutron slowing down material owing to have higher thermostability, higher hydrogen density, low neutron capture cross section and good heat-conducting and become the space.But in the zircoium hydride operating temperature range, hydrogen can constantly be separated out from zircoium hydride and be reduced its neutron moderating efficiency.Therefore, the hydrogen loss of control zircoium hydride under hot conditions is that the zircoium hydride moderator is applied to the major issue that the space heap is badly in need of solution.
Under the prerequisite of the use properties that does not influence body material, prepare the ceramic coating that the skim hydrogen diffusion coefficient is low, the surface recombination constant is low by process for treating surface at zirconium hydride surface, can effectively stop separating out of hydrogen in the matrix zircoium hydride.
At present, the method that adopts in-situ oxidation obtains oxide membranous layer at zirconium hydride surface and stops separating out of hydrogen in the zircoium hydride more.In addition, adopt electric plating method to prepare chromium coating and also can play the effect that suppresses hydrogen evolution in the zircoium hydride at zirconium hydride surface.
The resistance hydrogen rete that prepared in various methods goes out all has certain resistance hydrogen effect, but resistance hydrogen effect is unsatisfactory, mainly is that rete ftractures easily and peels off, thereby loses the provide protection to matrix because the thermal circulation performance of rete is low.In addition, because zircoium hydride fragility is very big, there are defectives such as a lot of tiny cracks matrix in itself, and this brings very big difficulty to preparing even, fine and close resistance hydrogen rete at zirconium hydride surface.So, only rely on the method that zirconium hydride surface prepares resistance hydrogen rete and also be difficult to solve the mistake hydrogen problem of zircoium hydride under hot conditions, also just be difficult to reach the service requirements of zircoium hydride slowing material.
Summary of the invention
One of purpose of the present invention provides a kind of preparation method of zircoium hydride, and this zircoium hydride can not separated out hydrogen under hot conditions.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of surface treatment method of zircoium hydride, its step is as follows:
(1), zircoium hydride is used acetone ultrasonic cleaning 15～20 minutes, oven dry;
(2), step (1) gained zircoium hydride is packed into Stainless Steel Crucible, put into then in the electron tubes type resistance furnace, vacuumize, in crucible, feed carbon dioxide again, be raised to 350～600 ℃ with 1～5 ℃/minute speed from room temperature, and in this temperature range, be incubated 30～60 hours;
(3), be cooled to room temperature, form at zirconium hydride surface and have certain anti-chemosmotic zirconium white rete of hydrogen.
Another object of the present invention provides a kind of method that prevents zircoium hydride hydrogen evolution under hot conditions.
Above-mentioned purpose of the present invention reaches by the following technical programs:
A kind of method that prevents zircoium hydride hydrogen evolution under hot conditions, its step is as follows:
(1), zircoium hydride is used acetone ultrasonic cleaning 15～20 minutes, oven dry;
(2), step (1) gained zircoium hydride is packed into Stainless Steel Crucible, put into then in the electron tubes type resistance furnace, vacuumize, in crucible, feed carbon dioxide again, be raised to 350～600 ℃ with 1～5 ℃/minute speed from room temperature, and in this temperature range, be incubated 30～60 hours;
(3), be cooled to room temperature, form at zirconium hydride surface and have certain anti-chemosmotic zirconium white rete of hydrogen;
(4), place the mixed atmosphere of oxidizing gas and rare gas element to heat the zircoium hydride after the above-mentioned oxidation, be heated to 500～900 ℃ of uses from room temperature.
A kind of optimal technical scheme is characterized in that: oxidizing gas is oxygen, carbonic acid gas or water vapour described in the described step (4); Described rare gas element is helium, argon gas or nitrogen, and described oxidizing gas shared volume percent in atmosphere is 5～100%, and all the other are rare gas element.
The present invention is by the variation of hydrogen dividing potential drop in the quadrupole mass spectrometer monitoring heat-processed, can reflect the dehydrogenation behavior of zircoium hydride by the variation of hydrogen dividing potential drop, and estimates the ability that the present invention stops hydrogen evolution with this.
The present invention makes the oxide film with the effect of certain resistance hydrogen by the method for in-situ oxidation in advance at zirconium hydride surface, and places the oxidizing atmosphere of definite composition to use the zircoium hydride after the oxidation.Experiment showed, that this method can solve the mistake hydrogen problem of zircoium hydride under hot conditions well.
Advantage that the inventive method has and beneficial effect: (1) utilizes the present invention can effectively stop the hydrogen evolution behavior of zircoium hydride when temperature more than 500 ℃ is used; (2) the present invention is not limited by zircoium hydride thermal shocking at work; (3) the inventive method is simple to operate, and production cost is low, and is not subjected to the restriction of zircoium hydride device shape and size.
Below by the drawings and specific embodiments the present invention is elaborated, but scope of the present invention is not constituted any limitation.
Description of drawings
Fig. 1 is the curve that changes gained in the embodiment of the invention 1 with hydrogen dividing potential drop in the quadrupole mass spectrometer monitoring heat-processed.
Fig. 2 is the curve that changes gained in the embodiment of the invention 2 with hydrogen dividing potential drop in the quadrupole mass spectrometer monitoring heat-processed.
Fig. 3 is the curve that changes gained in the embodiment of the invention 3 with hydrogen dividing potential drop in the quadrupole mass spectrometer monitoring heat-processed.
Fig. 4 is the curve that changes gained among the comparative example 1 of the present invention with hydrogen dividing potential drop in the quadrupole mass spectrometer monitoring heat-processed.
Embodiment
The hydrogen atomic percent zirconium is about 1.8 zircoium hydride and cuts into the cylindrical sample of Φ 20mm * 10mm.Sample is dried after 15 minutes through the acetone ultrasonic cleaning.
Pretreated zircoium hydride sample is put into the electron tubes type resistance furnace carry out the high-temperature thermal oxidation processing, make zirconium hydride surface generate zirconium white resistance hydrogen rete.Concrete steps are as follows: with the zircoium hydride sample Stainless Steel Crucible of packing into, put into then in the electron tubes type resistance furnace, start mechanical pump, vacuumize, the air in the crucible is extracted clean, feed CO then in crucible
2To 0.1MPa, begin heating.Heat-up rate in the heat-processed is 1 ℃/minute, when temperature reaches 350 ℃, is incubated 60 hours, cuts off the electricity supply then, and furnace cooling generates zirconium white resistance hydrogen rete.
Place the mixed gas of oxygen and helium to heat in the zircoium hydride sample after the oxidation, wherein the shared volume percent of oxygen is 5%, and Heating temperature is heated to 500 ℃ from room temperature, is incubated 1 hour.Change by hydrogen dividing potential drop in the quadrupole mass spectrometer monitoring heat-processed, the result as shown in Figure 1.
The hydrogen atomic percent zirconium is about 1.8 zircoium hydride and cuts into the cylindrical sample of Φ 20mm * 10mm.Sample, is dried after 20 minutes through the acetone ultrasonic cleaning.
Pretreated zircoium hydride sample is put into the electron tubes type resistance furnace carry out the high-temperature thermal oxidation processing, make zirconium hydride surface generate zirconium white resistance hydrogen rete.Concrete steps are as follows: with the zircoium hydride sample Stainless Steel Crucible of packing into, put into then in the electron tubes type resistance furnace, start mechanical pump, vacuumize, the air in the crucible is extracted clean, feed CO then in crucible
2To 0.1MPa, begin heating.Heat-up rate in the heat-processed is 5 ℃/minute, when temperature reaches 600 ℃, is incubated 30 hours, cuts off the electricity supply then, and furnace cooling generates zirconium white resistance hydrogen rete.
Place purity oxygen to heat in the zircoium hydride sample after the oxidation, promptly the shared volume percent of oxygen is 100%, and Heating temperature is heated to 900 ℃ from room temperature, is incubated 1 hour.Change by hydrogen dividing potential drop in the quadrupole mass spectrometer monitoring heat-processed, the result as shown in Figure 2.
The hydrogen atomic percent zirconium is about 1.8 zircoium hydride and cuts into the cylindrical sample of Φ 20mm * 10mm.Sample, is dried after 20 minutes through the acetone ultrasonic cleaning.
Pretreated zircoium hydride sample is put into the electron tubes type resistance furnace carry out the high-temperature thermal oxidation processing, make zirconium hydride surface generate zirconium white resistance hydrogen rete.Concrete steps are as follows: with the zircoium hydride sample Stainless Steel Crucible of packing into, put into then in the electron tubes type resistance furnace, start mechanical pump, vacuumize, the air in the crucible is extracted clean, feed CO then in crucible
2To 0.1MPa, begin heating.Heat-up rate in the heat-processed is 2 ℃/minute, when temperature reaches 500 ℃, is incubated 40 hours, cuts off the electricity supply then, and furnace cooling generates zirconium white resistance hydrogen rete.
Place the mixed gas of carbon dioxide and argon gas to heat in the zircoium hydride sample after the oxidation, wherein the shared volume percent of carbon dioxide is 50%, and Heating temperature is heated to 800 ℃ from room temperature, is incubated 1 hour.Change by hydrogen dividing potential drop in the quadrupole mass spectrometer monitoring heat-processed, the result as shown in Figure 3.
The comparative example 1
The hydrogen atomic percent zirconium is about 1.8 zircoium hydride and cuts into the cylindrical sample of Φ 20mm * 10mm.Sample is through the acetone ultrasonic cleaning after 20 minutes, and oven dry directly places pretreated zircoium hydride sample helium to carry out the dehydrogenation test then, with the present invention in embodiment compare.Heating temperature is a room temperature to 900 ℃ in the dehydrogenation experiment, and rate of heating is 10 ℃/minute.
Fig. 4 is the variation of zircoium hydride hydrogen dividing potential drop in heat-processed among the comparative example, contrasts as can be seen with each embodiment (Fig. 1-3), and the zircoium hydride that does not deal with after temperature is increased to 500 ℃, just has apparent in view hydrogen evolution phenomenon under the helium condition.And three embodiment of the present invention all do not detect the phenomenon of separating out of hydrogen in its heating and the insulating process subsequently in 600 ℃ to 900 ℃ temperature range, have confirmed that the present invention can effectively stop zircoium hydride hydrogen evolution behavior under hot conditions.
Claims (3)
1. the surface treatment method of a zircoium hydride, its step is as follows:
(1), zircoium hydride is used acetone ultrasonic cleaning 15～20 minutes, oven dry;
(2), step (1) gained zircoium hydride is packed into Stainless Steel Crucible, put into then in the electron tubes type resistance furnace, vacuumize, in crucible, feed carbon dioxide again, be raised to 350～600 ℃ with 1～5 ℃/minute speed from room temperature, and in this temperature range, be incubated 30～60 hours;
(3), be cooled to room temperature, form at zirconium hydride surface and have certain anti-chemosmotic zirconium white rete of hydrogen.
2. method that prevents zircoium hydride hydrogen evolution under hot conditions, its step is as follows:
(1), zircoium hydride is used acetone ultrasonic cleaning 15～20 minutes, oven dry;
(2), step (1) gained zircoium hydride is packed into Stainless Steel Crucible, put into then in the electron tubes type resistance furnace, vacuumize, in crucible, feed carbon dioxide again, be raised to 350～600 ℃ with 1～5 ℃/minute speed from room temperature, and in this temperature range, be incubated 30～60 hours;
(3), be cooled to room temperature, form at zirconium hydride surface and have certain anti-chemosmotic zirconium white rete of hydrogen;
(4), place the mixed atmosphere of oxidizing gas and rare gas element to heat the zircoium hydride after the above-mentioned oxidation, be heated to 500～900 ℃ of uses from room temperature.
3. according to the described method that prevents zircoium hydride hydrogen evolution under hot conditions of claim 2, it is characterized in that: oxidizing gas is oxygen, carbonic acid gas or water vapour described in the described step (4); Described rare gas element is helium, argon gas or nitrogen, and described oxidizing gas shared volume percent in atmosphere is 5～100%, and all the other are rare gas element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101042400A CN101559926B (en) | 2008-04-17 | 2008-04-17 | Method for preparing zirconium hydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101042400A CN101559926B (en) | 2008-04-17 | 2008-04-17 | Method for preparing zirconium hydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101559926A CN101559926A (en) | 2009-10-21 |
| CN101559926B true CN101559926B (en) | 2010-12-22 |
Family
ID=41218933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101042400A Active CN101559926B (en) | 2008-04-17 | 2008-04-17 | Method for preparing zirconium hydride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101559926B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001626B (en) * | 2010-11-16 | 2012-02-15 | 上海大学 | Method and device for preparing superfine zirconium hydride powder by continuous dynamic hydrogenation method |
| CN109273105B (en) * | 2018-09-13 | 2022-03-25 | 中国核动力研究设计院 | Supercritical carbon dioxide reactor fuel assembly |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1940144A (en) * | 2005-09-29 | 2007-04-04 | 中国核动力研究设计院 | Production of zirconium hydride surface Cr CO hydrogen penetration barrier layer |
| CN101134679A (en) * | 2007-08-17 | 2008-03-05 | 北京有色金属研究总院 | Method for preparing zirconium hydride surface hydrogen-proof pervious bed |
-
2008
- 2008-04-17 CN CN2008101042400A patent/CN101559926B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1940144A (en) * | 2005-09-29 | 2007-04-04 | 中国核动力研究设计院 | Production of zirconium hydride surface Cr CO hydrogen penetration barrier layer |
| CN101134679A (en) * | 2007-08-17 | 2008-03-05 | 北京有色金属研究总院 | Method for preparing zirconium hydride surface hydrogen-proof pervious bed |
Non-Patent Citations (2)
| Title |
|---|
| 刘庆生等.C02反应法制备氢化锆表面氢渗透阻挡层的研究.表面技术.2005,34(2),第32-34页. * |
| 单丽梅等.氢渗透阻挡层在CO2中的破坏.表面技术.2007,36(2),第12-13页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101559926A (en) | 2009-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103469173B (en) | The preparation method of hole conducting properties gallium oxide film and hole conducting properties gallium oxide film | |
| CN105541412A (en) | Preparation method of SiC nanowire-toughened SiC ceramic coating on surface of C/C composite | |
| CN101134679A (en) | Method for preparing zirconium hydride surface hydrogen-proof pervious bed | |
| CN101559926B (en) | Method for preparing zirconium hydride | |
| CN105932304A (en) | Preparation method for solid oxide fuel cell anode | |
| CN102773489A (en) | Method for preparing high-purity superfine vanadium, chromium and titanium mixed powder | |
| CN108305693A (en) | A kind of uranium nitride pellet preparation method | |
| CN101894594B (en) | Sub-stoichiometric UO2-xPreparation process of annular core block | |
| CN104835959B (en) | Lithium ferrous borate anode material of lithium ion battery and preparation method thereof | |
| CN107500767A (en) | Uranium carbide pellet and preparation method thereof, fuel rod | |
| CN111509082A (en) | Preparation method of gallium-doped polycrystalline silicon film and application of gallium-doped polycrystalline silicon film in solar cell | |
| EP0410420B1 (en) | Solid oxide fuel cell and method of manufacturing the same | |
| WO2017004818A1 (en) | Manufacturing equipment manufacturing silicon oxide compound and manufacturing method thereof | |
| CN101942701A (en) | Heat treatment method of solar-grade silicon crystal | |
| CN109659051B (en) | Preparation method of U-Zr-C fuel | |
| CN100551832C (en) | A kind of preparation high temperature nuclear reactor fuel element UO 2The method of nuclear core | |
| CN1211502C (en) | Method for preparing layer for guarding against pervasion of hydrogen on surface of stainless steel | |
| CN101651101A (en) | Silicon carbide ion activation annealing device and silicon carbide ion activation annealing method | |
| CN107299269B (en) | A kind of W-Cr-Al composite material and preparation method of resistance to high temperature oxidation | |
| CN106966699B (en) | Preparation method of high-temperature composite material full-temperature-section heat matching coating | |
| CN104909337A (en) | Lithium metaborate hydrogen storage composite material adulterated with lithium hydride and preparation method thereof | |
| CN104278231B (en) | Thermal oxidization hydrogen resistance method of Ti68Zr32 alloy | |
| CN103288074A (en) | Preparation method of nano new diamond powder | |
| CN116031475A (en) | Halide solid electrolyte and preparation method and application thereof | |
| CN108336306A (en) | A kind of preparation method of composite ceramics electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190626 Address after: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Research Institute of engineering and Technology Co., Ltd. Address before: 100088, 2, Xinjie street, Beijing Patentee before: General Research Institute for Nonferrous Metals |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210412 Address after: 101407 No.11, Xingke East Street, Yanqi Economic and Technological Development Zone, Huairou District, Beijing Patentee after: Youyan resources and Environment Technology Research Institute (Beijing) Co.,Ltd. Address before: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee before: YOUYAN ENGINEERING TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. |
|
| TR01 | Transfer of patent right |